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EP2459754B1 - Reformer gas based direct reduction process with recycling of reduction off gases and decarbonisation of recycled gas portion used as fuel gas for the reformer burner - Google Patents

Reformer gas based direct reduction process with recycling of reduction off gases and decarbonisation of recycled gas portion used as fuel gas for the reformer burner Download PDF

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Publication number
EP2459754B1
EP2459754B1 EP20100734103 EP10734103A EP2459754B1 EP 2459754 B1 EP2459754 B1 EP 2459754B1 EP 20100734103 EP20100734103 EP 20100734103 EP 10734103 A EP10734103 A EP 10734103A EP 2459754 B1 EP2459754 B1 EP 2459754B1
Authority
EP
European Patent Office
Prior art keywords
gas
dedusting
reduction
reformer
line
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP20100734103
Other languages
German (de)
French (fr)
Other versions
EP2459754A1 (en
Inventor
Robert Millner
Guenter Peer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Primetals Technologies Austria GmbH
Original Assignee
Siemens VAI Metals Technologies GmbH Austria
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Priority to PL10734103T priority Critical patent/PL2459754T3/en
Publication of EP2459754A1 publication Critical patent/EP2459754A1/en
Application granted granted Critical
Publication of EP2459754B1 publication Critical patent/EP2459754B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0006—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0073—Selection or treatment of the reducing gases
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/02—Making spongy iron or liquid steel, by direct processes in shaft furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/02—Making spongy iron or liquid steel, by direct processes in shaft furnaces
    • C21B13/029—Introducing coolant gas in the shaft furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
    • C21B2100/20—Increasing the gas reduction potential of recycled exhaust gases
    • C21B2100/22—Increasing the gas reduction potential of recycled exhaust gases by reforming
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
    • C21B2100/20—Increasing the gas reduction potential of recycled exhaust gases
    • C21B2100/28—Increasing the gas reduction potential of recycled exhaust gases by separation
    • C21B2100/282—Increasing the gas reduction potential of recycled exhaust gases by separation of carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
    • C21B2100/40—Gas purification of exhaust gases to be recirculated or used in other metallurgical processes
    • C21B2100/44—Removing particles, e.g. by scrubbing, dedusting
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
    • C21B2100/60—Process control or energy utilisation in the manufacture of iron or steel
    • C21B2100/64—Controlling the physical properties of the gas, e.g. pressure or temperature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • a method of reducing metal oxides to metallized material by contact with hot reducing gas produced by catalytically reforming a mixture of natural gas with the top gas withdrawn from the reduction unit, the combustible gas providing heat to the burners for the endothermic reforming processes occurring in the reforming a subset of the top gas obtained in the reduction of metal oxides to metallized material and natural gas is obtained, for example, in US Pat FIG. 1 of the WO2006135984 described. Due to ever stricter legal environmental regulations, the separation of CO 2 for generating a concentrated CO 2 stream from the resulting exhaust gases in the process is desired, with the possibility for later sequestration of the CO 2 stream before the thus treated exhaust gases are released into the environment.
  • the fuel gas for the reformer is burned with air as an oxygen source, and therefore, the combustion exhaust gas contains a large amount of nitrogen. Accordingly, the following systems for CO 2 removal from the combustion exhaust gas must be large. Moreover, for CO 2 removal from the combustion exhaust gas essentially only chemical Absorption process in question, which is characterized by a large size plant and high energy consumption, which is supplied for example via steam.
  • the metal oxides are iron oxides.
  • nickel, copper, lead, cobalt can be reduced.
  • Gaseous hydrocarbons are, for example, natural gas, methane, propane, syngas from coal gasification, coke oven gas.
  • gaseous hydrocarbons includes both the possibility that only one compound, for example pure propane, is present, as well as the possibility that a mixture of several compounds is present, for example a mixture of propane and methane.
  • the gas containing the carbon dioxide CO 2 and / or water vapor H 2 O is, for example, top gas from the process according to the invention for the reduction of metal oxides.
  • top gas is to be understood as the gas which is removed from the reduction unit in which the reduction of the metal oxides to metallized material takes place. Before the reforming, it is optionally still purified, for example by deposition of entrained dust and / or water.
  • the gas containing carbon dioxide CO 2 and / or water vapor H 2 O may also be, for example, export gas from another metal oxide reduction process, for example, smelting reduction process or syngas from a coal gasification process such as a Lurgi fixed bed gasifier or Siemens runaway gasifier.
  • it is top gas from the process according to the invention for the reduction of metal oxides.
  • Table 1 A typical composition of top gas from a direct reduction process is shown in Table 1: Table 1: Typical gas composition of DR Topgas Top gas composition after gas purification CO [Vol%] 20-25 CO 2 [Vol%] 15-20 H 2 [Vol%] 40-46 H 2 O [Vol%] 0-18 CH 4 [Vol%] 2-4 N 2 [Vol%] 1-2
  • the lower limit of the amount of carbon dioxide is CO 2 0% by volume, preferably 5% by volume, more preferably 15% by volume, and the upper limit of the amount of the amount Carbon dioxide CO 2 25% by volume, preferably 30% by volume, particularly preferably 40% by volume.
  • the lower limit of the amount of water vapor is H 2 O 0 vol%, preferably 10 vol%, and the upper limit of the amount of water vapor H 2 O 20 vol %, preferably 55% by volume.
  • a reducing gas which contains as reducing constituents mainly H 2 and CO. It is known that such a reforming is an endothermic reaction, for which reason heat is supplied to the reformer, for example, by combustion of fuel gas with oxygen in burners associated with the reformer.
  • the oxygen is supplied for example by air supply, supply of another oxygen-containing gas mixture, or supply of technically pure oxygen.
  • the fuel gas is at least partially obtained from a subset of the costs incurred in the reduction of metal oxides to metallized material top gas.
  • This top gas still contains combustible components such as CO and H 2 , which are used in the burners of the reformer to generate the heat necessary for the reforming.
  • the subset of the top gas from which the fuel gas is obtained is a CO conversion reaction, also called CO shift or water gas shift reaction, subjected.
  • This known reaction serves to reduce the CO content in the top gas and at the same time to increase the H 2 content, CO 2 being formed at the same time.
  • CO + H 2 O ⁇ CO 2 + H 2 ⁇ ⁇ H R 298 0 - 41 . 2 kJ / mol
  • the burners of the reformer a fuel gas is supplied, which contains as a combustible component mainly hydrogen H 2 . This has the advantage that less CO 2 is produced by combustion in the burners, since the proportion of CO 2 -producing CO components in the fuel gas is low.
  • the CO conversion reaction is preferably carried out according to high-temperature or crude gas conversion processes, since both processes do not have too high sensitivity to hydrogen sulfide (H 2 S) presence in the gas stream to be treated.
  • the CO conversion reaction is exothermic, but can also be conducted isothermally and thereby be used for example for the production of steam.
  • an inlet temperature of 160-450 ° C, in the high-temperature CO conversion process preferably 300-450 ° C, depending on the CO conversion process.
  • a heating to such temperatures must take place due to the associated temperature drop after the wet scrubbing.
  • the temperature of the top gas can be used equally for the subsequent CO conversion reaction.
  • cooling and CO 2 and H 2 O are separated from the gas stream of the conversion gas obtained in the CO conversion reaction. Since the gas flow of the conversion gas, in contrast to the combustion exhaust gas contains only a small amount of nitrogen, and CO 2 is present as correspondingly concentrated in the combustion exhaust gas, and since the CO 2 removal occurs prior to combustion, which is a CO 2 removal to be subjected to gas volume less than in a CO 2 removal from the combustion exhaust gas. Accordingly, the removal is less expensive.
  • CO 2 does not contribute to the calorific value of the fuel gas.
  • conventional methods for using top gas - which already contains CO 2 after the reduction of the metal oxides - in the fuel gas is therefore often an admixture of gaseous hydrocarbons, such as natural gas, necessary to the calorific value of the fuel gas to achieve the required flame temperature in the Reformer to increase the required level.
  • gaseous hydrocarbons such as natural gas
  • Due to the inventive removal of the CO 2 prior to combustion - and the concomitant increase in the calorific value of the fuel gas - can be dispensed with such an admixture of gaseous hydrocarbons in the rule.
  • an admixture of gaseous hydrocarbons as needed is still possible.
  • Such admixture may be such that gaseous hydrocarbons are added to the CO 2 lean conversion gas for the production of fuel gas.
  • gaseous hydrocarbons are added to the CO 2 lean conversion gas for the production of fuel gas.
  • the CO 2 lean conversion gas is not mixed with fuel gas before use, the low CO 2 conversion gas is the fuel gas.
  • the CO 2 lean conversion gas is slightly mixed, for example gaseous hydrocarbons, it is a component of the fuel gas.
  • seal gas is a non-flammable and inert gas used to seal the escape of process gas and to provide an inert atmosphere over a material. So-called seal gas is used for example in the raw material charging and in the shaft discharge of a reduction shaft, or in hot conveyors.
  • the gas obtained in the process according to the invention after any water separation from the combustion exhaust gas contains as the main component nitrogen and hardly CO 2 . In contrast, according to a procedure as in FIG.
  • combustion exhaust gas 18 to 20 vol% CO 2 which in contact with product of the reduction process, such as hot DRI (direct reduced iron), for example, in the shaft discharge of a reduction shaft or in Hot conveyors can lead to reoxidation and thus to product deterioration.
  • product of the reduction process such as hot DRI (direct reduced iron)
  • Hot conveyors can lead to reoxidation and thus to product deterioration.
  • Such a risk does not exist when using the inventively produced combustion exhaust gas as seal gas.
  • the conversion gas is cooled before the CO 2 removal in order to achieve a temperature necessary for CO 2 removal, preferably of 30-60 ° C.
  • a temperature necessary for CO 2 removal preferably of 30-60 ° C.
  • it is also freed from condensation introduced in the conversion reaction, but unreacted water vapor.
  • the dedusting can be done wet or dry.
  • the advantage of a dry dedusting is that the heat content for purposes of performing the CO conversion reaction necessary temperature can be used.
  • the outlet temperature of top gas from a reduction unit is typically in the range 250-500 ° C.
  • the heat content is used to generate steam, which is required for carrying out the CO conversion reaction. It is also advantageous if the steam required for carrying out the CO conversion reaction is recovered at other stations of the process according to the invention.
  • the top gas stream may need to be heated before the CO conversion reaction is carried out, in order to ensure a temperature of the gas stream necessary for the CO conversion reaction.
  • the dedusting can be carried out so that the entire top gas is dedusted, and after this dedusting a subset is diverted for the production of fuel gas, or it can be done after the diversion of the subset for the production of fuel gas dedusting.
  • the CO 2 removal in the resulting CO 2 can be, for example, compressed, condensed, and / or sequestered in order to reduce the CO 2 emissions of the process, which are released to the environment atmosphere.
  • the gaseous hydrocarbons are typically natural gas, methane, propane.
  • a hydrocarbon feed line for gaseous hydrocarbons opens into the connecting line, whereby, if necessary, the admixture of gaseous hydrocarbons can take place in order to obtain a fuel gas with the desired calorific value.
  • the hydrocarbon feed line for gaseous hydrocarbons can, viewed from the discharge line, open behind the CO 2 removal device into the connecting line.
  • the dedusting device is a dry dedusting device such as a cyclone, hot gas filter, bag filter.
  • the dedusting device is a wet dedusting device.
  • a gas heating device is preferably present in the connecting line between the wet dedusting device and the CO conversion reactor.
  • FIG. 1 be a reduction unit 1, here a fixed bed reduction shaft, 2 metal oxides 3 - in the present case iron oxides - are added via the Oxidzugabevorraum 2, for example as pellets or lumpy ore.
  • the discharge line 5 is the top gas which metallized in the reduction unit in the reduction of metal oxides Material from the reducing gas is produced, discharged from the reduction unit.
  • compressors 17a 17b are present in order to overcome the resulting pressure drop in the system.
  • a reformer 4 for the catalytic reforming of a mixture of top gas and gaseous hydrocarbons a mixture of top gas and gaseous hydrocarbons, in this case natural gas, are supplied via a mixture feed line 6.
  • the natural gas is supplied via the natural gas line 7.
  • the reformer 4 is provided with burners 8a, 8b, 8c for supplying heat necessary for the reforming by combustion of fuel gas.
  • the hot reducing gas formed in the reformer 4 is supplied via the reducing gas supply line 9 to the reduction unit 1.
  • a discharge line 10 for removing the resulting in the combustion of fuel gas in the reformer combustion exhaust gas the combustion exhaust gas is withdrawn from the reformer.
  • the combustion exhaust gas flows out of the reformer 4.
  • the exhaust duct 10 includes a device 11 for cooling the combustion exhaust gas and for releasing the combustion exhaust gas from water. Cooling and liberation of water take place in the same device.
  • the discharge line 10 leads into a chimney, through which the combustion exhaust gas can be released into the environment.
  • the burners 8a, 8b, 8c are provided with devices for supplying fuel gas, represented by the branching off from the discharge line 5 connecting line 12. Through the connecting line 12, the burners 8a, 8b, 8c fuel gas is supplied. Via the oxygen supply line 13 for the supply of oxygen - in this case by means of air supply - the burners 8a, 8b, 8c of the necessary for the combustion of the fuel gas oxygen is supplied. The air is fed by means of blower 14 in the oxygen supply line.
  • the discharge line 10 is a device for heating the guided in the oxygen supply line 13 air, in this case a recuperator 15 for indirect heat exchange of the air in the oxygen supply line 13 with the combustion exhaust gas in the discharge line 10, is present. Furthermore, in the discharge line 10 is a device for heating the mixture of top gas and gaseous hydrocarbons in the mixture supply line 6, in this case a recuperator 16 for indirect heat exchange between the mixture of top gas and gaseous hydrocarbons in the mixture supply line 6 and the combustion exhaust gas in the discharge line 10th , available. In the discharge line 5, a dedusting device 18, in this case a wet dedusting device, is present between the reduction unit 1 and the branch of the connecting line 12.
  • a gas heating device 19 in this case a recuperator for indirect heat exchange, a CO conversion reactor 20, a gas cooling device 21 and a CO 2 removal device 22 are seen from the branch from the discharge line 5 in succession.
  • a steam supply line 23 opens into the connecting line 12 in front of the CO conversion reactor 20.
  • An export of produced steam from the CO conversion reactor 20 is indicated by a dotted line starting from this.
  • An export of condensate from the gas cooling device 21 is represented by an outgoing from this arrow.
  • the export of a CO 2 -rich gas stream from the CO 2 removal arrangement 22 is represented by an outgoing from this dashed arrow.
  • the CO 2 -rich gas stream can be sequestered, for example.
  • a hydrocarbon feed line 24 for gaseous hydrocarbons opens into the connecting line 12.
  • the metal oxides 3 reduced in the reduction unit 1 are removed from the reduction unit 1, as indicated by an arrow.
  • the resulting in the reduction top gas is carried out through the discharge line 5 from the reduction unit.
  • a partial amount of the top gas is guided in the connecting line 12 to the burners 8 a, 8 b, 8 c, wherein it is first heated in the gas heating device 19 to a temperature necessary for the function of the CO conversion reactor 20 is, and is subjected to steam supply via the steam supply line 23 in the CO conversion reactor 20 of the CO conversion reaction.
  • the product thus obtained, called conversion gas is cooled in the gas cooling device 21 and freed of entrained vapor by condensation, and then released from CO 2 in the CO 2 removal device 22.
  • the low-CO 2 product of this step is used as a fuel gas after admixture of gaseous hydrocarbons by the hydrocarbon feed line 24 in the burners 8 a, 8 b, 8 c.
  • the oxygen required for combustion is supplied via the oxygen supply line 13 in the form of compressed air by means of blower 14.
  • hot reducing gas is prepared by reforming a mixture of top gas and gaseous hydrocarbons, and fed via the reducing gas supply line 9 to the reduction unit.
  • FIG. 4 shows a device analogous to FIG. 2 , with the difference that as gas, which contains carbon dioxide (CO 2 ) and / or water vapor (H 2 O, not top gas, but syngas from a coal gasification process with up to 40 vol% carbon dioxide and up to 55 vol% water vapor is used.
  • This syngas from a coal gasification process is introduced into the mixture feed line 6 via the syngas line 31 which opens into the mixture feed line 6.
  • the mixture of syngas and natural gas generated in the mixture feed line 6 is reformed in the reformer 4.
  • FIG. 4 across from FIG. 2 added device parts and the natural gas line 7 provided with reference numerals.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Industrial Gases (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Manufacture Of Iron (AREA)

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Reduktion von Metalloxiden zu metallisiertem Material durch Kontakt mit heißem Reduktionsgas, welches zumindest zum Teil durch katalytische Reformierung eines Gemisches von

  • einem Gas, welches Kohlendioxid (CO2) und/oder Wasserdampf (H2O enthält, mit
  • gasförmigen Kohlenwasserstoffen
hergestellt wird,
wobei das Brenngas für die Wärme für die bei der Reformierung ablaufenden endothermen Reformierungsprozesse liefernden Brenner zumindest teilweise aus einer Teilmenge des bei der Reduktion von Metalloxiden zu metallisiertem Material anfallenden Topgases gewonnen wird, wobei diese Teilmenge des Topgases vor ihrer Nutzung als Komponente des Brenngases zunächst einer Entstaubung und dann einer CO-Konvertierungsreaktion unterzogen wird, und das bei der CO-Konvertierungsreaktion erhaltene Konvertierungsgas nach einer Abkühlung einer CO2-Entfernung unterzogen wird. Weiterhin betrifft die vorliegende Erfindung eine Vorrichtung zur Durchführung des Verfahrens.The present invention relates to a process for the reduction of metal oxides to metallized material by contact with hot reducing gas which, at least in part, by catalytic reforming of a mixture of
  • a gas containing carbon dioxide (CO 2 ) and / or water vapor (H 2 O, with
  • gaseous hydrocarbons
will be produced,
wherein the fuel gas is obtained for the heat for the endothermic reforming process during the reforming burner at least partially from a subset of the resulting in the reduction of metal oxides to metallized material top gas, said subset of the top gas before their use as a component of the fuel gas first dedusting and then subjected to a CO conversion reaction, and the conversion gas obtained in the CO conversion reaction is subjected to CO 2 removal after cooling. Furthermore, the present invention relates to an apparatus for carrying out the method.

Ein Verfahren zur Reduktion von Metalloxiden zu metallisiertem Material durch Kontakt mit heißem Reduktionsgas, welches durch katalytische Reformierung eines Gemisches von Erdgas mit dem aus dem Reduktionsaggregat entnommenen Topgas hergestellt wird, wobei das Brenngas für die Wärme für die bei der Reformierung ablaufenden endothermen Reformierungsprozesse liefernden Brenner aus einer Teilmenge des bei der Reduktion von Metalloxiden zu metallisiertem Material anfallenden Topgases, und Erdgas gewonnen wird, ist beispielsweise in Figur 1 der WO2006135984 beschrieben. Aufgrund immer strenger werdender gesetzlicher Umweltvorschriften ist die Abtrennung von CO2 zur Erzeugung eines konzentrierten CO2 Stromes aus den bei den Verfahren entstehenden Abgasen gewünscht, mit der Möglichkeit zur späteren Sequestrierung des CO2 Stromes, bevor die so behandelten Abgase in die Umwelt entlassen werden. Bei einem Verfahren wie in WO2006135984 gezeigt wird das Brenngas für den Reformer mit Luft als Sauerstoffquelle verbrannt, weshalb das Verbrennungsabgas eine große Menge Stickstoff enthält. Entsprechend müssen nachfolgende Anlagen zur CO2-Entfernung aus dem Verbrennungsabgas groß dimensioniert sein. Zudem kommen für eine CO2-Entfernung aus dem Verbrennungsabgas im Wesentlichen nur chemische Absorptionsverfahren in Frage, welche sich durch eine große Anlagengröße und hohen Verbrauch an Energie, die beispielsweise über Dampf zugeführt wird, kennzeichnen.A method of reducing metal oxides to metallized material by contact with hot reducing gas produced by catalytically reforming a mixture of natural gas with the top gas withdrawn from the reduction unit, the combustible gas providing heat to the burners for the endothermic reforming processes occurring in the reforming a subset of the top gas obtained in the reduction of metal oxides to metallized material and natural gas is obtained, for example, in US Pat FIG. 1 of the WO2006135984 described. Due to ever stricter legal environmental regulations, the separation of CO 2 for generating a concentrated CO 2 stream from the resulting exhaust gases in the process is desired, with the possibility for later sequestration of the CO 2 stream before the thus treated exhaust gases are released into the environment. In a method such as in WO2006135984 As shown, the fuel gas for the reformer is burned with air as an oxygen source, and therefore, the combustion exhaust gas contains a large amount of nitrogen. Accordingly, the following systems for CO 2 removal from the combustion exhaust gas must be large. Moreover, for CO 2 removal from the combustion exhaust gas essentially only chemical Absorption process in question, which is characterized by a large size plant and high energy consumption, which is supplied for example via steam.

Verfahren und Vorrichtungen zur Direktreduktion von Eisenerz in Schachtöfen sind beispielsweise aus den Dokumenten DE 26 51 309 A1 und WO 2006/135984 A1 bekannt.Methods and devices for the direct reduction of iron ore in shaft furnaces are, for example, from the documents DE 26 51 309 A1 and WO 2006/135984 A1 known.

Es ist die Aufgabe der vorliegenden Erfindung, ein Verfahren bereitzustellen, welches die Vermeidung von CO2 in dem Verbrennungsabgas mit kleineren Anlagen - mit entsprechend geringeren Verbrauchszahlen - und anderen CO2-Entfernungsverfahren ermöglicht, sowie eine Vorrichtung zur Durchführung des Verfahrens.It is the object of the present invention to provide a method which enables the avoidance of CO 2 in the combustion exhaust gas with smaller plants - with correspondingly lower consumption figures - and other CO 2 removal processes, and an apparatus for carrying out the method.

Diese Aufgabe wird gelöst durch Verfahren zur Reduktion von Metalloxiden zu metallisiertem Material durch Kontakt mit heißem Reduktionsgas, wobei das Reduktionsgas zumindest zum Teil durch katalytische Reformierung eines Gemisches von

  • einem Gas, das Kohlendioxid (CO2) und/oder Wasserdampf (H2O) enthält, mit
  • gasförmigen Kohlenwasserstoffen
hergestellt wird, wobei die Wärme für die bei der Reformierung ablaufenden endothermen Reformierungsprozesse zumindest teilweise durch Verbrennung eines Brenngases geliefert wird, und das dabei entstehende Verbrennungsabgas abgezogen wird, wobei das Brenngas zumindest teilweise aus einer Teilmenge des bei der Reduktion von Metalloxiden zu metallisiertem Material anfallenden Topgases, gewonnen wird, dadurch gekennzeichnet, dass die Teilmenge des Topgases, aus der das Brenngas gewonnen wird, zunächst einer Entstaubung und dann einer CO-Konvertierungsreaktion unterzogen wird, und das bei der CO-Konvertierungsreaktion erhaltene Konvertierungsgas nach einer Abkühlung einer CO2-Entfernung unterzogen wird, und das dabei anfallende CO2-arme-Konvertierungsgas zumindest als Komponente des Brenngases genutzt wird.This object is achieved by methods for the reduction of metal oxides to metallized material by contact with hot reducing gas, wherein the reducing gas, at least in part by catalytic reforming of a mixture of
  • a gas containing carbon dioxide (CO 2 ) and / or water vapor (H 2 O), with
  • gaseous hydrocarbons
is produced, wherein the heat for the running during the reforming endothermic reforming processes is at least partially supplied by combustion of a fuel gas, and the resulting combustion exhaust gas is withdrawn, the fuel gas at least partially from a subset of the resulting in the reduction of metal oxides to metallized material top gas is obtained, characterized in that the subset of the top gas from which the fuel gas is recovered, first a dedusting and then a CO conversion reaction is subjected, and the conversion gas obtained in the CO conversion reaction after cooling a CO 2 removal is used, and the resulting low CO 2 conversion gas is used at least as a component of the fuel gas.

Bevorzugterweise handelt es sich bei den Metalloxiden um Eisenoxide. Weiters können aber auch gemäß Richardson-Jeffes Diagramm beispielsweise Nickel, Kupfer, Blei, Kobalt reduziert werden.Preferably, the metal oxides are iron oxides. Furthermore, according to Richardson-Jeffes diagram, for example, nickel, copper, lead, cobalt can be reduced.

Das Reduktionsgas wird zumindest zum Teil durch katalytische Reformierung eines Gemisches von

  • einem Gas, das Kohlendioxid CO2 und/oder Wasserdampf H2O enthält, mit
  • gasförmigen Kohlenwasserstoffen
hergestellt. Diese Reformierung erfolgt durch zumindest teilweise Umsetzung der gasförmigen Kohlenwasserstoffe mit H2O und CO2 zu Wasserstoff (H2) und Kohlenmonoxid (CO). Die für die Reformierung benötigten Substanzen H2O und/oder CO2 können dem Gemisch zur Reformierung jeweils einzeln oder zusammen zugegeben werden, und/oder es wird das in dem Gas, das Kohlendioxid CO2 und/oder Wasserdampf H2O enthält, vorhandene H2O und/oder CO2 genutzt. Bevorzugt ist es, dem Gemisch zumindest H2O - als Wasserdampf - zuzugeben.The reducing gas is at least in part by catalytic reforming of a mixture of
  • a gas containing carbon dioxide CO 2 and / or water vapor H 2 O, with
  • gaseous hydrocarbons
produced. This reforming is carried out by at least partial reaction of the gaseous hydrocarbons with H 2 O and CO 2 to hydrogen (H 2 ) and carbon monoxide (CO). The substances H 2 O and / or CO 2 required for the reforming can each be added to the mixture for reforming individually or together, and / or it is present in the gas containing carbon dioxide CO 2 and / or water vapor H 2 O. H 2 O and / or CO 2 used. It is preferred to add at least H 2 O - as water vapor - to the mixture.

Unter gasförmigen Kohlenwasserstoffen sind beispielsweise Erdgas, Methan, Propan, Syngas aus Kohlevergasung, Koksofengas zu verstehen. Der Begriff gasförmige Kohlenwasserstoffe umfasst sowohl die Möglichkeit, dass lediglich eine Verbindung, beispielsweise reines Propan, vorliegt, als auch die Möglichkeit, dass ein Gemisch aus mehreren Verbindungen vorliegt, beispielsweise ein Gemisch aus Propan und Methan.Gaseous hydrocarbons are, for example, natural gas, methane, propane, syngas from coal gasification, coke oven gas. The term gaseous hydrocarbons includes both the possibility that only one compound, for example pure propane, is present, as well as the possibility that a mixture of several compounds is present, for example a mixture of propane and methane.

Das Gas, das das Kohlendioxid CO2 und/oder Wasserdampf H2O enthält, ist beispielsweise Topgas aus dem erfindungsgemäßen Verfahren zur Reduktion von Metalloxiden. Unter Topgas ist dabei das Gas zu verstehen, welches aus dem Reduktionsaggregat, in dem die Reduktion der Metalloxide zu metallisiertem Material stattfindet, abgeführt wird. Vor der Reformierung wird es gegebenenfalls noch gereinigt, beispielsweise durch Abscheidung von mitgeführtem Staub und/oder Wasser.
Das Gas, das Kohlendioxid CO2 und/oder Wasserdampf H2O enthält, kann beispielsweise auch Exportgas aus einem anderen Verfahren zur Reduktion von Metalloxiden sein, beispielseise Schmelzreduktionsverfahren, oder Syngas aus einem Kohlevergasungsverfahren wie beispielsweise einem Lurgi Festbettvergaser oder Siemens Flugstromvergaser.
Bevorzugt ist es Topgas aus dem erfindungsgemäßen Verfahren zur Reduktion von Metalloxiden.The gas containing the carbon dioxide CO 2 and / or water vapor H 2 O is, for example, top gas from the process according to the invention for the reduction of metal oxides. Under top gas is to be understood as the gas which is removed from the reduction unit in which the reduction of the metal oxides to metallized material takes place. Before the reforming, it is optionally still purified, for example by deposition of entrained dust and / or water.
The gas containing carbon dioxide CO 2 and / or water vapor H 2 O may also be, for example, export gas from another metal oxide reduction process, for example, smelting reduction process or syngas from a coal gasification process such as a Lurgi fixed bed gasifier or Siemens runaway gasifier.
Preferably, it is top gas from the process according to the invention for the reduction of metal oxides.

Eine typische Zusammensetzung von Topgas aus einem Direktreduktionsverfahren ist in Tabelle 1 gezeigt: Tabelle 1: Typische Gaszusammensetzung von DR Topgas Topgaszusammensetzung nach Gasreinigung CO [vol%] 20-25 CO2 [vol%] 15-20 H2 [vol%] 40-46 H2O [vol%] 0-18 CH4 [vol%] 2-4 N2 [vol%] 1-2 A typical composition of top gas from a direct reduction process is shown in Table 1: Table 1: Typical gas composition of DR Topgas Top gas composition after gas purification CO [Vol%] 20-25 CO 2 [Vol%] 15-20 H 2 [Vol%] 40-46 H 2 O [Vol%] 0-18 CH 4 [Vol%] 2-4 N 2 [Vol%] 1-2

In dem Gas, das Kohlendioxid CO2 und/oder Wasserdampf H2O enthält, beträgt die Untergrenze der Menge an Kohlendioxid CO2 0 Vol%, bevorzugt 5 Vol%, besonders bevorzugt 15 Vol%, und die Obergrenze der Menge an der Menge an Kohlendioxid CO2 25 Vol%, bevorzugt 30 Vol%, besonders bevorzugt 40 Vol%.In the gas containing carbon dioxide CO 2 and / or water vapor H 2 O, the lower limit of the amount of carbon dioxide is CO 2 0% by volume, preferably 5% by volume, more preferably 15% by volume, and the upper limit of the amount of the amount Carbon dioxide CO 2 25% by volume, preferably 30% by volume, particularly preferably 40% by volume.

In dem Gas, das Kohlendioxid CO2 und/oder Wasserdampf H2O enthält, beträgt die Untergrenze der Menge an Wasserdampf H2O 0 Vol%, bevorzugt 10 Vol%, und die Obergrenze der Menge an der Menge Wasserdampf H2O 20 Vol%, bevorzugt 55 Vol%.In the gas containing carbon dioxide CO 2 and / or water vapor H 2 O, the lower limit of the amount of water vapor is H 2 O 0 vol%, preferably 10 vol%, and the upper limit of the amount of water vapor H 2 O 20 vol %, preferably 55% by volume.

Durch die katalytische Reformierung wird ein Reduktionsgas erhalten, welches als reduzierende Bestandteile hauptsächlich H2 und CO enthält. Es ist bekannt, dass es sich bei einer solchen Reformierung um eine endotherme Reaktion handelt, weshalb dem Reformer beispielsweise durch Verbrennung von Brenngas mit Sauerstoff, in Brennern, die dem Reformer zugeordnet sind, Wärme zugeführt wird. Der Sauerstoff wird beispielsweise geliefert durch Luftzufuhr, Zufuhr eines anderen sauerstoffhaltigen Gasgemisches, oder Zufuhr von technisch reinem Sauerstoff.By the catalytic reforming, a reducing gas is obtained, which contains as reducing constituents mainly H 2 and CO. It is known that such a reforming is an endothermic reaction, for which reason heat is supplied to the reformer, for example, by combustion of fuel gas with oxygen in burners associated with the reformer. The oxygen is supplied for example by air supply, supply of another oxygen-containing gas mixture, or supply of technically pure oxygen.

Zur Erhöhung der Effizienz des Gesamtverfahrens wird das Brenngas zumindest teilweise aus einer Teilmenge des bei der Reduktion von Metalloxiden zu metallisiertem Material anfallenden Topgases, gewonnen. Dieses Topgas enthält noch brennbare Bestandteile wie beispielsweise CO und H2, die in den Brennern des Reformers zur Erzeugung der für die Reformierung notwendigen Wärme genutzt werden.To increase the efficiency of the overall process, the fuel gas is at least partially obtained from a subset of the costs incurred in the reduction of metal oxides to metallized material top gas. This top gas still contains combustible components such as CO and H 2 , which are used in the burners of the reformer to generate the heat necessary for the reforming.

Erfindungsgemäß wird die Teilmenge des Topgases, aus der das Brenngas gewonnen wird, einer CO-Konvertierungsreaktion, auch genannt CO-Shift- oder Wassergas-Shift-Reaktion, unterzogen. Diese bekannte Reaktion dient dazu, den CO-Anteil im Topgas zu vermindern und gleichzeitig den H2 -Anteil zu erhöhen, wobei gleichzeitig CO2 gebildet wird.

        CO + H2O ⇄ CO2 + H2

Δ ⁢ H R 298 0 = - 41 , 2 kJ / mol

Figure imgb0001
According to the invention, the subset of the top gas from which the fuel gas is obtained is a CO conversion reaction, also called CO shift or water gas shift reaction, subjected. This known reaction serves to reduce the CO content in the top gas and at the same time to increase the H 2 content, CO 2 being formed at the same time.

CO + H 2 O ⇄ CO 2 + H 2

Δ ⁢ H R 298 0 = - 41 . 2 kJ / mol
Figure imgb0001

Nach der CO-Konvertierungsreaktion erfolgt erfindungsgemäß eine Kühlung und Entfernung des CO2 und H2O Gehaltes in einer CO2 Entfernungsanlage, bevor eine Nutzung als Brenngas erfolgt. Dabei wird das CO2 bereits vor der Verbrennung effizient abgeschieden. Entsprechend kann der zur Entfernung von CO2 aus dem Verbrennungsabgas notwendige Aufwand reduziert werden.
Durch diese Maßnahmen wird den Brennern des Reformers ein Brenngas zugeführt, welches als brennbare Komponente hauptsächlich Wasserstoff H2 enthält. Das hat den Vorteil, dass in den Brennern weniger CO2 durch Verbrennung entsteht, da der Anteil an bei der Verbrennung CO2-generierenden CO Komponenten im Brenngas gering ist.According to the invention, after the CO conversion reaction, cooling and removal of the CO 2 and H 2 O content take place in a CO 2 removal plant, before they are used as fuel gas. At the same time, CO 2 is efficiently separated before combustion. Accordingly, the effort required to remove CO 2 from the combustion exhaust gas can be reduced.
By these measures, the burners of the reformer, a fuel gas is supplied, which contains as a combustible component mainly hydrogen H 2 . This has the advantage that less CO 2 is produced by combustion in the burners, since the proportion of CO 2 -producing CO components in the fuel gas is low.

Die CO-Konvertierungsreaktion erfolgt bevorzugterweise gemäß Hochtemperatur- oder Rohgaskonvertierungsverfahren, da beide Verfahren keine allzu hohe Empfindlichkeit gegenüber Schwefelwasserstoff (H2S) -Anwesenheit im zu behandelnden Gasstrom aufweisen.
Die CO-Konvertierungsreaktion ist exotherm, kann aber auch isotherm geführt und dabei beispielsweise zur Erzeugung von Dampf genutzt werden. Zum Betrieb des CO-Konvertierungsreaktors ist je nach CO-Konvertierungsverfahren eine Eintrittstemperatur von 160-450°C, beim Hochtemperatur CO-Konvertierungsverfahren bevorzugterweise 300-450°C, einzuhalten. Im Falle einer Nasswäsche des Topgases vor der CO-Konvertierungsreaktion muss aufgrund des damit verbundenen Temperaturabfalls nach der Nasswäsche eine Aufheizung auf solche Temperaturen erfolgen. Im Falle einer Trockenentstaubung des Topgases vor der CO-Konvertierungsreaktion kann die Temperatur des Topgases gleich für die nachfolgende CO-Konvertierungsreaktion verwendet werden.The CO conversion reaction is preferably carried out according to high-temperature or crude gas conversion processes, since both processes do not have too high sensitivity to hydrogen sulfide (H 2 S) presence in the gas stream to be treated.
The CO conversion reaction is exothermic, but can also be conducted isothermally and thereby be used for example for the production of steam. For operation of the CO conversion reactor, an inlet temperature of 160-450 ° C, in the high-temperature CO conversion process preferably 300-450 ° C, depending on the CO conversion process. In the case of a wet scrubbing of the top gas before the CO conversion reaction, a heating to such temperatures must take place due to the associated temperature drop after the wet scrubbing. In the case of dry dedusting of the top gas before the CO conversion reaction, the temperature of the top gas can be used equally for the subsequent CO conversion reaction.

Erfindungsgemäß wird im Anschluss an die CO-Konvertierungsreaktion gekühlt und CO2 sowie H2O aus dem Gasstrom des bei der CO-Konvertierungs-Reaktion erhaltenen Konvertierungsgases abgeschieden. Da der Gasstrom des Konvertierungsgases im Gegensatz zum Verbrennungsabgas nur eine geringe Stickstoffmenge enthält, und das CO2 entsprechend konzentrierter vorliegt als im Verbrennungsabgas, und weil die CO2-Entfernung vor der Verbrennung erfolgt, ist das einer CO2-Entfernung zu unterziehende Gasvolumen geringer als bei einer CO2-Entfernung aus Verbrennungsabgas. Entsprechend ist die Entfernung weniger aufwändig.According to the invention, following the CO conversion reaction, cooling and CO 2 and H 2 O are separated from the gas stream of the conversion gas obtained in the CO conversion reaction. Since the gas flow of the conversion gas, in contrast to the combustion exhaust gas contains only a small amount of nitrogen, and CO 2 is present as correspondingly concentrated in the combustion exhaust gas, and since the CO 2 removal occurs prior to combustion, which is a CO 2 removal to be subjected to gas volume less than in a CO 2 removal from the combustion exhaust gas. Accordingly, the removal is less expensive.

CO2 liefert keinen Beitrag zum Brennwert des Brenngases. Bei herkömmlichen Verfahren zur Nutzung von Topgas - welches nach der Reduktion der Metalloxide bereits CO2 enthält - im Brenngas ist daher oft eine Zumischung von gasförmigen Kohlenwasserstoffen, wie beispielsweise Erdgas, notwendig, um den Heizwert des Brenngases auf ein für die Erreichung der erforderlichen Flammentemperatur im Reformer erforderliches Maß anzuheben. Aufgrund der erfindungsgemäßen Entfernung des CO2 vor der Verbrennung - und der damit einhergehenden Erhöhung des Heizwertes des Brenngases - kann in der Regel auf solch eine Zumischung von gasförmigen Kohlenwasserstoffen verzichtet werden. Selbstverständlich ist eine Zumischung von gasförmigen Kohlenwasserstoffen bei Bedarf weiterhin möglich.CO 2 does not contribute to the calorific value of the fuel gas. In conventional methods for using top gas - which already contains CO 2 after the reduction of the metal oxides - in the fuel gas is therefore often an admixture of gaseous hydrocarbons, such as natural gas, necessary to the calorific value of the fuel gas to achieve the required flame temperature in the Reformer to increase the required level. Due to the inventive removal of the CO 2 prior to combustion - and the concomitant increase in the calorific value of the fuel gas - can be dispensed with such an admixture of gaseous hydrocarbons in the rule. Of course, an admixture of gaseous hydrocarbons as needed is still possible.

Eine solche Zumischung kann so erfolgen, dass dem CO2-armen-Konvertierungsgas zur Herstellung von Brenngas gasförmige Kohlenwasserstoffe zugemischt werden.
Wenn dem CO2-arme-Konvertierungsgas vor der Nutzung als Brenngas nichts zugemischt wird, ist das CO2-arme-Konvertierungsgas das Brenngas. Wenn dem CO2-arme-Konvertierungsgas etwas zugemischt wird, beispielsweise gasförmige Kohlenwasserstoffe, ist es eine Komponente des Brenngases.Such admixture may be such that gaseous hydrocarbons are added to the CO 2 lean conversion gas for the production of fuel gas.
When the CO 2 lean conversion gas is not mixed with fuel gas before use, the low CO 2 conversion gas is the fuel gas. When the CO 2 lean conversion gas is slightly mixed, for example gaseous hydrocarbons, it is a component of the fuel gas.

Ein weiterer Vorteil der Erfindung besteht darin, dass das Verbrennungsabgas nach einer gegebenenfalls erfolgten Wasserabscheidung vorzüglich als Sealgas genutzt werden kann. Als Sealgas bezeichnet man ein nicht brennbares und inertes Gas zur Abdichtung von Austritt von Prozessgas und zur Bereitstellung einer inerten Atmosphäre über einem Material. Sogenanntes Sealgas wird beispielsweise bei der Rohstoffchargierung und im Schachtaustrag eines Reduktionsschachtes, oder bei Heißförderern genutzt. Das bei dem erfindungsgemäßen Verfahren nach gegebenenfalls erfolgten Wasserabscheidung aus dem Verbrennungsabgas erhaltene Gas enthält als Hauptbestandteil Stickstoff und kaum CO2. Im Gegensatz dazu enthält nach einem Verfahren wie in Figur 1 der WO2006135984 gezeigt anfallendes Verbrennungsabgas 18 bis 20 Vol% CO2 , welches bei Kontakt mit Produkt des Reduktionsverfahrens, beispielsweise heißem DRI (direct reduced iron) beispielsweise im Schachtaustrag eines Reduktionsschachtes oder in Heißförderern zu Rückoxidation und damit zu Produktverschlechterung führen kann. Eine solche Gefahr besteht bei Verwendung des erfindungsgemäß anfallenden Verbrennungsabgases als Sealgas nicht.Another advantage of the invention is that the combustion exhaust gas can be used after an optionally made water separation excellent as a seal gas. Seal gas is a non-flammable and inert gas used to seal the escape of process gas and to provide an inert atmosphere over a material. So-called seal gas is used for example in the raw material charging and in the shaft discharge of a reduction shaft, or in hot conveyors. The gas obtained in the process according to the invention after any water separation from the combustion exhaust gas contains as the main component nitrogen and hardly CO 2 . In contrast, according to a procedure as in FIG. 1 of the WO2006135984 shown combustion exhaust gas 18 to 20 vol% CO 2 , which in contact with product of the reduction process, such as hot DRI (direct reduced iron), for example, in the shaft discharge of a reduction shaft or in Hot conveyors can lead to reoxidation and thus to product deterioration. Such a risk does not exist when using the inventively produced combustion exhaust gas as seal gas.

Aufgrund der hohen Temperatur des entstehenden Konvertierungsgases ist es bei dem erfindungsgemäßen Verfahren notwendig, dass das Konvertierungsgas vor der CO2-Entfernung gekühlt wird, um eine für die CO2-Entfernung notwendige Temperatur, bevorzugterweise von 30-60°C, zu erreichen. Vorzugsweise wird es auch von bei der Konvertierungsreaktion eingebrachtem, aber nicht umgesetztem Wasserdampf durch Kondensation befreit.Due to the high temperature of the resulting conversion gas, it is necessary in the method according to the invention that the conversion gas is cooled before the CO 2 removal in order to achieve a temperature necessary for CO 2 removal, preferably of 30-60 ° C. Preferably, it is also freed from condensation introduced in the conversion reaction, but unreacted water vapor.

Weiterhin ist es notwendig, die Teilmenge des Topgases, aus der Brenngas gewonnen wird, vor der CO-Konvertierungsreaktion zu entstauben um den Wartungsaufwand aufgrund von Ablagerungen und Schädigung von Anlagenkomponenten, niedrig zu halten, eine hohe Verfügbarkeit der Anlage zu gewährleisten, sowie die Umweltvorschriften für in die Umwelt entlassen Gase bezüglich Staubgehalt einzuhalten. Die Entstaubung kann nass oder trocken erfolgen. Der Vorteil einer trockenen Entstaubung besteht darin, dass der Wärmeinhalt für Zwecke der Durchführung der CO-Konvertierungsreaktion notwendige Temperatur genutzt werden kann. Die Austrittstemperatur von Topgas aus einem Reduktionsaggregat liegt typischerweise im Bereich 250-500°C. Zur optimalen Temperaturführung für die nachfolgenden Verfahrensschritte kann es erforderlich sein, die Temperatur noch etwas durch Kühlung, Heizung, oder Verdampfung von Wasser einzustellen. Vorteilhafterweise wird der Wärmeinhalt zur Erzeugung von Dampf, welcher für die Durchführung der CO-Konvertierungsreaktion benötigt wird, genutzt. Es ist auch vorteilhaft, wenn der Dampf, welcher für die Durchführung der CO-Konvertierungsreaktion benötigt wird, an anderen Stationen des erfindungsgemäßen Verfahrens gewonnen wird.Furthermore, it is necessary to dedust the subset of the top gas, is derived from the fuel gas before the CO conversion reaction to keep the maintenance costs due to deposits and damage to system components, low, to ensure high availability of the system, as well as environmental regulations for released into the environment to comply with gases regarding dust content. The dedusting can be done wet or dry. The advantage of a dry dedusting is that the heat content for purposes of performing the CO conversion reaction necessary temperature can be used. The outlet temperature of top gas from a reduction unit is typically in the range 250-500 ° C. For optimal temperature control for the subsequent process steps, it may be necessary to adjust the temperature somewhat by cooling, heating, or evaporation of water. Advantageously, the heat content is used to generate steam, which is required for carrying out the CO conversion reaction. It is also advantageous if the steam required for carrying out the CO conversion reaction is recovered at other stations of the process according to the invention.

Im Fall einer Nassentstaubung muss vor der Durchführung der CO-Konvertierungs-Reaktion gegebenenfalls eine Erwärmung des Topgasstromes erfolgen, um eine für die CO-Konvertierungsreaktion notwendige Temperatur des Gasstromes zu gewährleisten.In the case of wet dedusting, the top gas stream may need to be heated before the CO conversion reaction is carried out, in order to ensure a temperature of the gas stream necessary for the CO conversion reaction.

Die Entstaubung kann so erfolgen, dass das gesamte Topgas entstaubt wird, und nach dieser Entstaubung eine Teilmenge zur Gewinnung von Brenngas abgezweigt wird, oder es kann die Entstaubung nach der Abzweigung der Teilmenge zur Gewinnung von Brenngas erfolgen.The dedusting can be carried out so that the entire top gas is dedusted, and after this dedusting a subset is diverted for the production of fuel gas, or it can be done after the diversion of the subset for the production of fuel gas dedusting.

Das bei der CO2-Entfernung anfallende CO2 kann beispielsweise verdichtet, kondensiert und/oder sequestriert werden, um die CO2-Emissionen des Verfahrens, welche an die Umweltatmosphäre abgegeben werden, zu senken.The CO 2 removal in the resulting CO 2 can be, for example, compressed, condensed, and / or sequestered in order to reduce the CO 2 emissions of the process, which are released to the environment atmosphere.

Ein weiterer Gegenstand der vorliegenden Erfindung ist eine Vorrichtung zur Durchführung eines erfindungsgemäßen Verfahrens, mit einem Reduktionsaggregat zur Reduktion von Metalloxiden zu metallisiertem Material, einem Reformer zur Durchführung katalytischer Reformierung eines Gemisches von

  • einem Gas, welches Kohlendioxid (CO2) und/oder Wasserdampf (H2O) enthält, mit
  • gasförmigen Kohlenwasserstoffen,
wobei der Reformer mit einer Gemischzufuhrleitung zur Zufuhr des Gemisches versehen ist, und wobei der Reformer mit Brennern zur Lieferung von Wärme durch Verbrennung von Brenngas versehen ist, welche mit einer Sauerstoffzufuhrleitung verbunden sind, einer Abzugsleitung zum Abziehen von Verbrennungsabgas aus dem Reformer, einer Reduktionsgaszufuhrleitung für heißes Reduktionsgas aus dem Reformer in das Reduktionsaggregat,
einer Abfuhrleitung zur Abfuhr von Topgas aus dem Reduktionsaggregat, wobei die Brenner über eine von der Abfuhrleitung abzweigende Verbindungsleitung mit der Abfuhrleitung verbunden sind, und
wobei zumindest
in der Abfuhrleitung zwischen Reduktionsaggregat und der von ihr abzweigenden Verbindungsleitung,
oder in der Verbindungsleitung eine Entstaubungsvorrichtung vorhanden ist, dadurch gekennzeichnet, dass in der Verbindungsleitung, zwischen der gegebenenfalls vorhandenen Entstaubungseinrichtung und den Brennern, von der Abfuhrleitung aus gesehen aufeinanderfolgend ein CO-Konvertierungs-Reaktor, eine Gaskühlungsvorrichtung, und eine CO2-Entfernungs-Vorrichtung vorhanden sind.Another object of the present invention is an apparatus for carrying out a method according to the invention, comprising a reduction unit for the reduction of metal oxides to metallized material, a reformer for carrying out catalytic reforming of a mixture of
  • a gas containing carbon dioxide (CO 2 ) and / or water vapor (H 2 O), with
  • gaseous hydrocarbons,
wherein the reformer is provided with a mixture supply line for supplying the mixture, and wherein the reformer is provided with burners for supplying heat by combustion of fuel gas connected to an oxygen supply line, a discharge line for removing combustion exhaust gas from the reformer, a reducing gas supply line for hot reducing gas from the reformer into the reduction unit,
a discharge line for the removal of top gas from the reduction unit, wherein the burners are connected via a branching off from the discharge line connecting line to the discharge line, and
at least
in the discharge line between the reduction unit and the connecting line branching off from it,
or in the connecting line a dedusting device is present, characterized in that in the connecting line between the optionally existing dedusting and the burners, as seen from the discharge line sequentially a CO conversion reactor, a gas cooling device, and a CO 2 removal device available.

Bei den gasförmige Kohlenwasserstoffen handelt es sich typischerweise um Erdgas, Methan, Propan.The gaseous hydrocarbons are typically natural gas, methane, propane.

Nach einer Ausführungsform mündet eine Kohlenwasserstoffzuleitung für gasförmige Kohlenwasserstoffe in die Verbindungsleitung, wodurch bei Bedarf die Zumischung von gasförmigen Kohlenwasserstoffen erfolgen kann, um ein Brenngas mit gewünschtem Heizwert zu erhalten.According to one embodiment, a hydrocarbon feed line for gaseous hydrocarbons opens into the connecting line, whereby, if necessary, the admixture of gaseous hydrocarbons can take place in order to obtain a fuel gas with the desired calorific value.

Dabei kann die Kohlenwasserstoffzuleitung für gasförmige Kohlenwasserstoffen von der Abfuhrleitung aus gesehen hinter der CO2-Entfernungs-Vorrichtung in die Verbindungsleitung münden.The hydrocarbon feed line for gaseous hydrocarbons can, viewed from the discharge line, open behind the CO 2 removal device into the connecting line.

Nach einer Ausführungsform ist die Entstaubungsvorrichtung eine Trockenentstaubungsvorrichtung wie beispielsweise ein Zyklon, Heißgasfilter, Schlauchfilter.In one embodiment, the dedusting device is a dry dedusting device such as a cyclone, hot gas filter, bag filter.

Nach einer anderen Ausführungsform ist die Entstaubungsvorrichtung eine Nassentstaubungsvorrichtung.In another embodiment, the dedusting device is a wet dedusting device.

Es kann auch mehr als eine Einstaubungsvorrichtung vorhanden sein. Diese können beispielsweise sowohl
in der Abfuhrleitung zwischen Reduktionsaggregat und der von ihr abzweigenden Verbindungsleitung,
und in der Verbindungsleitung angeordnet sein.
Gemäß einer Ausführungsform ist dabei beispielsweise eine Nassentstaubungsvorrichtung in der Abfuhrleitung zwischen Reduktionsaggregat und der von ihr abzweigenden Verbindungsleitung, und eine Trockenentstaubungsvorrichtung in der Verbindungsleitung angeordnet.There may also be more than one dusting device. These can be both
in the discharge line between the reduction unit and the connecting line branching off from it,
and be arranged in the connection line.
According to one embodiment, in this case, for example, a wet dedusting device is arranged in the discharge line between the reduction unit and the connecting line branching from it, and a dry dedusting device is arranged in the connecting line.

Dabei ist bevorzugterweise zwischen der Nassentstaubungsvorrichtung und dem CO-Konvertierungs-Reaktor eine Gaserwärmungsvorrichtung in der Verbindungsleitung vorhanden.In this case, a gas heating device is preferably present in the connecting line between the wet dedusting device and the CO conversion reactor.

Im Folgenden wird die vorliegende Erfindung anhand mehrerer schematischer Figuren näher erklärt.

  • Figur 1 zeigt eine erfindungsgemäße Vorrichtung, bei der eine Nassentstaubung vorhanden ist.
  • Figur 2 zeigt eine erfindungsgemäße Vorrichtung mit kombinierter Naß- und Trockenentstaubung.
  • Figur 3 zeigt eine erfindungsgemäße Vorrichtung mit reiner Trockenentstaubung und Kühlung des Topgases.
  • Figur 4 zeigt ein Verfahren entsprechend Figur 2, wobei das Gas, welches Kohlendioxid (CO2) und/oder Wasserdampf (H2O enthält, aus einer anderen Quelle als in Figur 2 stammt.
In the following, the present invention will be explained in more detail with reference to several schematic figures.
  • FIG. 1 shows a device according to the invention, in which a wet dedusting is present.
  • FIG. 2 shows a device according to the invention with combined wet and dry dedusting.
  • FIG. 3 shows a device according to the invention with pure dry dedusting and cooling of the top gas.
  • FIG. 4 shows a method accordingly FIG. 2 wherein the gas containing carbon dioxide (CO 2 ) and / or water vapor (H 2 O) from a source other than in FIG. 2 comes.

In Figur 1 werden einem Reduktionsaggregat 1, hier einem Festbettreduktionsschacht, werden über die Oxidzugabevorrichtung 2 Metalloxide 3 - im vorliegenden Fall Eisenoxide - zugegeben, beispielsweise als Pellets oder stückiges Erz. Über die Abfuhrleitung 5 wird das Topgas, welches in dem Reduktionsaggregat bei der Reduktion der Metalloxide zu metallisiertem Material aus dem Reduktionsgas entsteht, aus dem Reduktionsaggregat abgeführt. In der Abfuhrleitung 5 sind Verdichter 17a 17b vorhanden, um den in der Anlage entstehenden Druckabfall zu überwinden. In einen Reformer 4 zur katalytischen Reformierung eines Gemisches aus Topgas und gasförmigen Kohlenwasserstoffen werden über eine Gemischzufuhrleitung 6 ein Gemisch von Topgas und gasförmige Kohlenwasserstoffe, in diesem Fall Erdgas, zugeführt. Das Erdgas wird dabei über die Erdgasleitung 7 zugeführt. Der Reformer 4 ist mit Brennern 8a, 8b, 8c zur Lieferung von für die Reformierung notwendiger Wärme durch Verbrennung von Brenngas versehen. Das im Reformer 4 gebildete heiße Reduktionsgas wird über die Reduktionsgaszufuhrleitung 9 dem Reduktionsaggregat 1 zugeführt. Über eine Abzugsleitung 10 zum Abziehen des bei der Verbrennung von Brenngas im Reformer anfallenden Verbrennungsabgases wird das Verbrennungsabgas aus dem Reformer abgezogen. Das Verbrennungsabgas strömt dabei aus dem Reformer 4 heraus.
Die Abzugsleitung 10 enthält eine Vorrichtung 11 zum Kühlen des Verbrennungsabgases und zur Befreiung des Verbrennungsabgases von Wasser. Kühlung und Befreiung von Wasser erfolgen in derselben Vorrichtung. Die Abzugsleitung 10 führt in einen Kamin, durch den das Verbrennungsabgas in die Umwelt entlassen werden kann.In FIG. 1 be a reduction unit 1, here a fixed bed reduction shaft, 2 metal oxides 3 - in the present case iron oxides - are added via the Oxidzugabevorrichtung 2, for example as pellets or lumpy ore. Via the discharge line 5 is the top gas which metallized in the reduction unit in the reduction of metal oxides Material from the reducing gas is produced, discharged from the reduction unit. In the discharge line 5 compressors 17a 17b are present in order to overcome the resulting pressure drop in the system. In a reformer 4 for the catalytic reforming of a mixture of top gas and gaseous hydrocarbons, a mixture of top gas and gaseous hydrocarbons, in this case natural gas, are supplied via a mixture feed line 6. The natural gas is supplied via the natural gas line 7. The reformer 4 is provided with burners 8a, 8b, 8c for supplying heat necessary for the reforming by combustion of fuel gas. The hot reducing gas formed in the reformer 4 is supplied via the reducing gas supply line 9 to the reduction unit 1. About a discharge line 10 for removing the resulting in the combustion of fuel gas in the reformer combustion exhaust gas, the combustion exhaust gas is withdrawn from the reformer. The combustion exhaust gas flows out of the reformer 4.
The exhaust duct 10 includes a device 11 for cooling the combustion exhaust gas and for releasing the combustion exhaust gas from water. Cooling and liberation of water take place in the same device. The discharge line 10 leads into a chimney, through which the combustion exhaust gas can be released into the environment.

Durch die Vorrichtung 11 oder durch weitere Prozessabwärmen, beispielsweise aus Topgas oder dem Konvertierungsgas nach der CO-Konvertierung. kann auch Dampf produziert werden, der für die CO Konvertierung genutzt werden kann.
Die Brenner 8a, 8b, 8c sind mit Vorrichtungen zur Zuführung von Brenngas, dargestellt durch die von der Abfuhrleitung 5 abzweigende Verbindungsleitung 12, versehen. Durch die Verbindungsleitung 12 wird den Brennern 8a, 8b, 8c Brenngas zugeleitet.
Über die Sauerstoffzufuhrleitung 13 zur Zufuhr von Sauerstoff - in diesem Fall mittels Luftzufuhr - wird den Brennern 8a, 8b, 8c der für die Verbrennung des Brenngases notwendige Sauerstoff zugeführt. Die Luft wird mittels Gebläse 14 in die Sauerstoffzufuhrleitung eingespeist.By the device 11 or by further process waste heat, for example from top gas or the conversion gas after the CO conversion. Steam can also be produced, which can be used for CO conversion.
The burners 8a, 8b, 8c are provided with devices for supplying fuel gas, represented by the branching off from the discharge line 5 connecting line 12. Through the connecting line 12, the burners 8a, 8b, 8c fuel gas is supplied.
Via the oxygen supply line 13 for the supply of oxygen - in this case by means of air supply - the burners 8a, 8b, 8c of the necessary for the combustion of the fuel gas oxygen is supplied. The air is fed by means of blower 14 in the oxygen supply line.

In der Abzugsleitung 10 ist eine Vorrichtung zur Erwärmung der in der Sauerstoffzufuhrleitung 13 geführten Luft, in diesem Fall ein Rekuperator 15 für indirekten Wärmeaustausch der Luft in der Sauerstoffzufuhrleitung 13 mit dem Verbrennungsabgas in der Abzugsleitung 10, vorhanden.
Weiterhin ist in der Abzugsleitung 10 eine Vorrichtung zur Erwärmung des Gemisches aus Topgas und gasförmigen Kohlenwasserstoffen in der Gemischzufuhrleitung 6, in diesem Fall ein Rekuperator 16 für indirekten Wärmeaustausch zwischen dem Gemisch aus Topgas und gasförmigen Kohlenwasserstoffen in der Gemischzufuhrleitung 6 und dem Verbrennungsabgas in der Abzugsleitung 10, vorhanden.
In der Abfuhrleitung 5 ist zwischen Reduktionsaggregat 1 und der Abzweigung der Verbindungsleitung 12 eine Entstaubungsvorrichtung 18, in diesem Fall eine Nassentstaubungsvorrichtung, vorhanden.
In der Verbindungsleitung 12 sind von der Abzweigung aus der Abfuhrleitung 5 aus gesehen hintereinander eine Gaserwärmungsvorrichtung 19, in diesem Fall ein Rekuperator zum indirekten Wärmeaustausch, ein CO-Konvertierungs-Reaktor 20, eine Gaskühlungsvorrichtung 21 und eine CO2-Entfernungsvorrichtung 22 vorhanden.
Von der Abzweigung aus der Abfuhrleitung 5 aus gesehen mündet dabei vor dem CO-Konvertierungs-Reaktor 20 eine Dampfzufuhrleitung 23 in die Verbindungsleitung 12. Eine Ausfuhr von produziertem Dampf aus dem CO-Konvertierungs-Reaktor 20 ist mit einem von diesem ausgehenden strichlierten Pfeil angedeutet. Eine Ausfuhr von Kondensat aus der Gaskühlungsvorrichtung 21 ist durch einen von dieser ausgehenden Pfeil dargestellt. Die Ausfuhr eines CO2-reichen Gasstromes aus der CO2-Entfernungsvorrichtung 22 ist durch einen von dieser ausgehenden strichlierten Pfeil dargestellt. Der CO2-reiche Gasstrom kann beispielsweise sequestriert werden.In the discharge line 10 is a device for heating the guided in the oxygen supply line 13 air, in this case a recuperator 15 for indirect heat exchange of the air in the oxygen supply line 13 with the combustion exhaust gas in the discharge line 10, is present.
Furthermore, in the discharge line 10 is a device for heating the mixture of top gas and gaseous hydrocarbons in the mixture supply line 6, in this case a recuperator 16 for indirect heat exchange between the mixture of top gas and gaseous hydrocarbons in the mixture supply line 6 and the combustion exhaust gas in the discharge line 10th , available.
In the discharge line 5, a dedusting device 18, in this case a wet dedusting device, is present between the reduction unit 1 and the branch of the connecting line 12.
In the connecting line 12, a gas heating device 19, in this case a recuperator for indirect heat exchange, a CO conversion reactor 20, a gas cooling device 21 and a CO 2 removal device 22 are seen from the branch from the discharge line 5 in succession.
As seen from the diversion from the discharge line 5, a steam supply line 23 opens into the connecting line 12 in front of the CO conversion reactor 20. An export of produced steam from the CO conversion reactor 20 is indicated by a dotted line starting from this. An export of condensate from the gas cooling device 21 is represented by an outgoing from this arrow. The export of a CO 2 -rich gas stream from the CO 2 removal arrangement 22 is represented by an outgoing from this dashed arrow. The CO 2 -rich gas stream can be sequestered, for example.

Von der Abfuhrleitung aus gesehen hinter der CO2-Entfernungsvorrichtung 22 mündet eine Kohlenwasserstoffzuleitung 24 für gasförmige Kohlenwasserstoffe in die Verbindungsleitung 12.As seen from the discharge line behind the CO 2 removal device 22, a hydrocarbon feed line 24 for gaseous hydrocarbons opens into the connecting line 12.

Die im Reduktionsaggregat 1 reduzierten Metalloxide 3 werden, wie durch einen Pfeil angedeutet, aus dem Reduktionsaggregat 1 entnommen.
Das bei der Reduktion anfallende Topgas wird durch die Abfuhrleitung 5 aus dem Reduktionsaggregat ausgeführt. Nach der Entstaubung in der Entstaubungsvorrichtung 5 wird eine Teilmenge des Topgases in der Verbindungsleitung 12 zu den Brennern 8a, 8b, 8c geführt, wobei es zunächst in der Gaserwärmungsvorrichtung 19 auf eine Temperatur erwärmt wird, die zur Funktion des CO-Konvertierungs-Reaktors 20 notwendig ist, und nach Dampfzufuhr über die Dampfzufuhrleitung 23 im CO-Konvertierungs-Reaktors 20 der CO-Konvertierungsreaktion unterworfen wird. Das dabei erhaltene Produkt, genannt Konvertierungsgas, wird in der Gaskühlungsvorrichtung 21 gekühlt und durch Kondensation von mitgeführten Dampf befreit, und anschließend in der CO2-Entfernungsvorrichtung 22 von CO2 befreit. Das CO2-arme Produkt dieses Schrittes, genannt CO2-armes-Konvertierungsgas, wird nach Zumischung von gasförmigen Kohlenwasserstoffen durch die Kohlenwasserstoffzuleitung 24 in den Brennern 8a, 8b, 8c als Brenngas verwendet. Der zur Verbrennung notwendige Sauerstoff wird über die Sauerstoffzufuhrleitung 13 in Form von mittels Gebläse 14 komprimierter Luft zugeführt. Im Reformer 4 wird heißes Reduktionsgas durch Reformierung eines Gemisches aus Topgas und gasförmiger Kohlenwasserstoffe hergestellt, und über die Reduktionsgaszufuhrleitung 9 dem Reduktionsaggregat zugeleitet.The metal oxides 3 reduced in the reduction unit 1 are removed from the reduction unit 1, as indicated by an arrow.
The resulting in the reduction top gas is carried out through the discharge line 5 from the reduction unit. After dedusting in the dedusting device 5, a partial amount of the top gas is guided in the connecting line 12 to the burners 8 a, 8 b, 8 c, wherein it is first heated in the gas heating device 19 to a temperature necessary for the function of the CO conversion reactor 20 is, and is subjected to steam supply via the steam supply line 23 in the CO conversion reactor 20 of the CO conversion reaction. The product thus obtained, called conversion gas, is cooled in the gas cooling device 21 and freed of entrained vapor by condensation, and then released from CO 2 in the CO 2 removal device 22. The low-CO 2 product of this step, called low CO 2 conversion gas, is used as a fuel gas after admixture of gaseous hydrocarbons by the hydrocarbon feed line 24 in the burners 8 a, 8 b, 8 c. The oxygen required for combustion is supplied via the oxygen supply line 13 in the form of compressed air by means of blower 14. In the reformer 4 hot reducing gas is prepared by reforming a mixture of top gas and gaseous hydrocarbons, and fed via the reducing gas supply line 9 to the reduction unit.

Figur 2 zeigt eine Vorrichtung analog zu Figur 1, wobei der Unterschied besteht, dass keine Entstaubungsvorrichtung 18 und keine Gaserwärmungsvorrichtung 19 vorhanden sind. Stattdessen sind

  • in der Abfuhrleitung 5 vom Reduktionsaggregat 1 aus gesehen hinter der Abzweigung der Verbindungsleitung 12 eine Entstaubungsvorrichtung 25, die als Nassentstaubungsvorrichtung ausgeführt ist, und
  • in der Verbindungsleitung 12 zwischen der Abzweigung der Verbindungsleitung 12 aus der Abfuhrleitung 5 und dem CO-Konvertierungsraktor 20 eine Entstaubungsvorrichtung 26, die als Trockenentstaubungsvorrichtung ausgeführt ist,
vorhanden. Da in der Entstaubungsvorrichtung 26 kein Temperaturverlust auftritt, ist keine Gaserwärmungsvorrichtung 19 zur Gewährleistung der für den CO-Konvertierungsreaktor notwendigen Temperatur notwendig. Zur besseren Übersichtlichkeit sind nur die in Figur 2 gegenüber Figur 1 hinzugekommenen Vorrichtungsteile mit Bezugszeichen versehen. FIG. 2 shows a device analogous to FIG. 1 with the difference that there is no dedusting device 18 and no gas heating device 19. Instead are
  • seen in the discharge line 5 from the reduction unit 1 from behind the junction of the connecting line 12, a dedusting device 25, which is designed as a wet dedusting, and
  • in the connecting line 12 between the branch of the connecting line 12 from the discharge line 5 and the CO conversion tractor 20, a dedusting device 26, which is designed as a dry dedusting device,
available. Since no temperature loss occurs in dedusting device 26, no gas heating device 19 is necessary to ensure the temperature necessary for the CO conversion reactor. For clarity, only the in FIG. 2 across from FIG. 1 added device parts provided with reference numerals.

Figur 3 zeigt eine Vorrichtung analog zu Figur 1, wobei der Unterschied darin besteht, dass keine Entstaubungsvorrichtung 18 und keine Gaserwärmungsvorrichtung 19 vorhanden sind.
Stattdessen sind

  • in der Abfuhrleitung 5 vom Reduktionsaggregat 1 aus gesehen vor der Abzweigung der Verbindungsleitung 12 eine Entstaubungsvorrichtung 27, die als Trockenentstaubungsvorrichtung ausgeführt ist, und
  • in der Abfuhrleitung 5 vom Reduktionsaggregat 1 aus gesehen hinter der Abzweigung der Verbindungsleitung 12 eine Vorrichtung zur Kühlung des Topgases, umfassend das als Rekuperator ausgeführte Kühlelement 28 und den mit Kühlwasser 29 betriebenen Gaskühler 30,
vorhanden.
Da in der Entstaubungsvorrichtung 27 kein Temperaturverlust auftritt, ist keine Gaserwärmungsvorrichtung 19 zur Gewährleistung der für den CO-Konvertierungsreaktor notwendigen Temperatur notwendig. Zur besseren Übersichtlichkeit sind nur die in Figur 2 gegenüber Figur 1 hinzugekommenen Vorrichtungsteile mit Bezugszeichen versehen. FIG. 3 shows a device analogous to FIG. 1 , the difference being that there is no dedusting device 18 and no gas heating device 19.
Instead are
  • seen in the discharge line 5 from the reduction unit 1 before the junction of the connecting line 12, a dedusting 27, which is designed as a dry dedusting, and
  • in the discharge line 5 from the reduction unit 1 from behind the branch of the connecting line 12, a device for cooling the top gas, comprising the designed as a recuperator cooling element 28 and operated with cooling water 29 gas cooler 30,
available.
Since no temperature loss occurs in dedusting device 27, no gas heating device 19 is necessary to ensure the temperature necessary for the CO conversion reactor. For clarity, only the in FIG. 2 across from FIG. 1 added device parts provided with reference numerals.

Figur 4 zeigt eine Vorrichtung analog zu Figur 2, mit dem Unterschied, dass als Gas, welches Kohlendioxid (CO2) und/oder Wasserdampf (H2O enthält, nicht Topgas, sondern Syngas aus einem Kohlevergasungsverfahren mit bis zu 40 Vol% Kohlendioxid und bis zu 55 Vol% Wasserdampf verwendet wird. Dieses Syngas aus einem nicht dargestellten Kohlevergasungsverfahren wird über die in die Gemischzufuhrleitung 6 mündende Syngasleitung 31 in die Gemischzufuhrleitung 6 eingeleitet. Das in der Gemischzufuhrleitung 6 dabei generierte Gemisch von Syngas und Erdgas wird im Reformer 4 reformiert. Zur besseren Übersichtlichkeit sind nur die in Figur 4 gegenüber Figur 2 hinzugekommenen Vorrichtungsteile sowie die Erdgasleitung 7 mit Bezugszeichen versehen. FIG. 4 shows a device analogous to FIG. 2 , with the difference that as gas, which contains carbon dioxide (CO 2 ) and / or water vapor (H 2 O, not top gas, but syngas from a coal gasification process with up to 40 vol% carbon dioxide and up to 55 vol% water vapor is used. This syngas from a coal gasification process, not shown, is introduced into the mixture feed line 6 via the syngas line 31 which opens into the mixture feed line 6. The mixture of syngas and natural gas generated in the mixture feed line 6 is reformed in the reformer 4. For clarity, only the in FIG. 4 across from FIG. 2 added device parts and the natural gas line 7 provided with reference numerals.

Bezugszeichenliste:LIST OF REFERENCE NUMBERS

11
Reduktionsaggregatreduction unit
22
OxidzugabevorrichtungOxidzugabevorrichtung
33
Metalloxidemetal oxides
44
Reformerreformer
55
Abfuhrleitungdischarge line
66
GemischzufuhrleitungMixture supply line
77
Erdgasleitungnatural gas pipeline
8a, 8b, 8c8a, 8b, 8c
Brennerburner
99
ReduktionsgaszufuhrleitungReducing gas supply line
1010
Abzugsleitungwithdrawal line
1111
Vorrichtung zum Kühlen/Befreiung von H2OApparatus for cooling / releasing H 2 O
1212
Verbindungsleitungconnecting line
1313
SauerstoffzufuhrleitungOxygen supply line
1414
Kompressorcompressor
1515
Rekuperatorrecuperator
1616
Rekuperatorrecuperator
17a, 17b17a, 17b
Verdichtercompressor
1818
Entstaubungsvorrichtungdedusting
1919
GaserwärmungsvorrichtungGas heater
2020
CO-KonvertierungsreaktorCO conversion reactor
2121
GaskühlungsvorrichtungGas cooling device
2222
CO2-EntfernungsvorrichtungCO 2 removal device
2323
DampfzufuhrleitungSteam supply line
2424
Erdgaszuleitungnatural gas supply
2525
Entstaubungsvorrichtungdedusting
2626
Entstaubungsvorrichtungdedusting
2727
Entstaubungsvorrichtungdedusting
2828
Kühlelementcooling element
2929
Kühlwassercooling water
3030
Gaskühlergas cooler
3131
SyngasleitungSyngasleitung

Claims (14)

  1. Process for the reduction of metal oxides to form metalized material by contact with hot reducing gas, wherein the reducing gas is produced at least partially by catalytic reformation of a mixture of
    - a gas containing carbon dioxide (CO2) and/or steam (H2O) with
    - gaseous hydrocarbons,
    wherein the heat for the endothermal reformation processes which take place during the reformation is provided at least partially by the combustion of a fuel gas, and the combustion off-gas produced in the process is drawn off, wherein the fuel gas is obtained at least partially from a partial quantity of the top gas produced during the reduction of metal oxides to form metalized material, and the partial quantity of the top gas, from which the fuel gas is obtained, is subjected to dedusting, characterized in that the partial quantity of the top gas, from which the fuel gas is obtained and which has been subjected to dedusting, is, after dedusting, subjected to a CO conversion reaction, and the conversion gas obtained during the CO conversion reaction is subjected to CO2 removal after cooling, and the CO2-depleted conversion gas produced in the process is used at least as a component of the fuel gas.
  2. Process according to Claim 1, characterized in that the gas containing carbon dioxide (CO2) and/or steam (H2O) is top gas from the process for the reduction of metal oxides.
  3. Process according to Claim 1, characterized in that the gas containing carbon dioxide (CO2) and/or steam (H2O) is export gas from a smelting reduction process or syngas from a coal gasification process.
  4. Process according to Claims 1 to 3, characterized in that gaseous hydrocarbons are admixed to the CO2-depleted conversion gas in order to obtain fuel gas.
  5. Process according to one of the preceding claims, characterized in that the dedusting takes place in dry form.
  6. Process according to one of Claims 1 to 4, characterized in that the dedusting takes place in wet form.
  7. Apparatus for carrying out a process according to one of Claims 1 to 6, having a reduction unit (1) for the reduction of metal oxides (3) to form metalized material, having a reformer (4) for carrying out catalytic reformation of a mixture of
    - a gas containing carbon dioxide (CO2) and/or steam (H2O) with
    - gaseous hydrocarbons,
    wherein the reformer (4) is provided with a mixture supply line (6) for supplying the mixture, and wherein the reformer is provided with burners (8a, 8b, 8c), which are connected to an oxygen supply line (13), for providing heat by the combustion of fuel gas,
    having a drawing-off line (10) for drawing off combustion off-gas from the reformer (4),
    having a reducing gas supply line (9) for hot reducing gas from the reformer (4) into the reduction unit (1),
    having a discharge line (5) for discharging top gas from the reduction unit (1),
    wherein the burners (8a, 8b, 8c) are connected to the discharge line (5) via a connection line (12) which branches off from the discharge line (5), and wherein a dedusting apparatus (18) is present at least in the discharge line (5) between the reduction unit (1) and the connection line (12) which branches off from it, or in the connection line (12),
    characterized in that a CO conversion reactor (20), a gas cooling apparatus (21) and a CO2 removal apparatus (22) are present in succession, as seen from the discharge line (5), in the connection line (12), between the dedusting device (18) which may be present and the burners (8a, 8b, 8c).
  8. Apparatus according to Claim 7, characterized in that a hydrocarbon feed line (24) for gaseous hydrocarbons issues into the connection line (12).
  9. Apparatus according to Claim 8, characterized in that the hydrocarbon feed line (24) for gaseous hydrocarbons issues into the connection line (12) downstream from the CO2 removal apparatus (22), as seen from the discharge line (5).
  10. Apparatus according to one of Claims 7 to 9, characterized in that the dedusting apparatus (18) is a dry-dedusting apparatus.
  11. Apparatus according to one of Claims 7 to 9, characterized in that the dedusting apparatus (18) is a wet-dedusting apparatus.
  12. Apparatus according to Claim 11, characterized in that a gas heating apparatus (19) is present in the connection line between the wet-dedusting apparatus and the CO conversion reactor (20).
  13. Apparatus according to one of Claims 7 to 12, characterized in that the reduction unit (1) is a fluidized bed cascade.
  14. Apparatus according to one of Claims 7 to 12, characterized in that the reduction unit (1) is a fixed-bed reduction shaft.
EP20100734103 2009-07-31 2010-07-14 Reformer gas based direct reduction process with recycling of reduction off gases and decarbonisation of recycled gas portion used as fuel gas for the reformer burner Not-in-force EP2459754B1 (en)

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PCT/EP2010/060130 WO2011012448A1 (en) 2009-07-31 2010-07-14 Reformed gas-based reduction method with return of the waste reduction gases and decarbonisation of the waste gas component used as combustion gas for the reformer

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RU2532202C2 (en) 2014-10-27
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WO2011012448A1 (en) 2011-02-03
CA2769398C (en) 2017-06-20
EP2459754A1 (en) 2012-06-06
US20120174710A1 (en) 2012-07-12
CA2769398A1 (en) 2011-02-03
US9169535B2 (en) 2015-10-27
MX2011013415A (en) 2012-02-21
CN102471810A (en) 2012-05-23
AU2010278183B2 (en) 2013-11-28
KR20120038017A (en) 2012-04-20
CN105567898A (en) 2016-05-11
PL2459754T3 (en) 2015-05-29
AT508523A1 (en) 2011-02-15
US9797026B2 (en) 2017-10-24
SA110310620B1 (en) 2014-04-08
RU2012107479A (en) 2013-09-10
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JP2013501137A (en) 2013-01-10
US20150329930A1 (en) 2015-11-19

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